Calcium vapor adsorption on the metal-organic framework NU-1000: Structure and energetics

James M. Lownsbury, Iván A. Santos-López, Wei Zhang, Charles T. Campbell, Haoyu S. Yu, Wei Guang Liu, Christopher J. Cramer, Donald G. Truhlar, Timothy Wang, Joseph T Hupp, Omar K. Farha

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The nature and energy of the reactions between calcium vapor and the internal surfaces of the metal-organic framework (MOF) NU-1000 have been studied by adsorption microcalorimetry, low energy He+ ion scattering spectroscopy (LEIS), X-ray photoelectron spectroscopy (XPS), and Kohn-Sham density functional theory (DFT). NU-1000 is one of the most stable MOFs with transition-metal-oxide nodes, and thus it is of interest as a potential catalyst or catalytic support when modified with other metals. The reaction heats of Ca with NU-1000 are high below 2 monolayers (ML) Ca coverage (570-366 kJ/mol), attributed (based on DFT) to Ca reacting first with free benzoic acid functionalities or water impurities, then with H2O and OH groups on the Zr6 nodes to produce Ca(OH)2 clusters. With higher Ca doses, the heat of Ca reaction decreases asymptotically to the sublimation enthalpy of bulk Ca (178 kJ/mol), attributed to the formation of Ca(solid) nanoparticles on the external surface, which only occurs after all of the H2O and OH groups are titrated deeply enough (∼20 nm) such that slow Ca diffusion prevents further reaction.

Original languageEnglish
Pages (from-to)16850-16862
Number of pages13
JournalJournal of Physical Chemistry C
Volume120
Issue number30
DOIs
Publication statusPublished - Aug 4 2016

Fingerprint

Density functional theory
calcium
Calcium
Metals
Vapors
vapors
Adsorption
adsorption
Benzoic Acid
Benzoic acid
Sublimation
Catalyst supports
metals
Oxides
Transition metals
Enthalpy
Monolayers
X ray photoelectron spectroscopy
Spectroscopy
Scattering

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Lownsbury, J. M., Santos-López, I. A., Zhang, W., Campbell, C. T., Yu, H. S., Liu, W. G., ... Farha, O. K. (2016). Calcium vapor adsorption on the metal-organic framework NU-1000: Structure and energetics. Journal of Physical Chemistry C, 120(30), 16850-16862. https://doi.org/10.1021/acs.jpcc.6b05707

Calcium vapor adsorption on the metal-organic framework NU-1000 : Structure and energetics. / Lownsbury, James M.; Santos-López, Iván A.; Zhang, Wei; Campbell, Charles T.; Yu, Haoyu S.; Liu, Wei Guang; Cramer, Christopher J.; Truhlar, Donald G.; Wang, Timothy; Hupp, Joseph T; Farha, Omar K.

In: Journal of Physical Chemistry C, Vol. 120, No. 30, 04.08.2016, p. 16850-16862.

Research output: Contribution to journalArticle

Lownsbury, JM, Santos-López, IA, Zhang, W, Campbell, CT, Yu, HS, Liu, WG, Cramer, CJ, Truhlar, DG, Wang, T, Hupp, JT & Farha, OK 2016, 'Calcium vapor adsorption on the metal-organic framework NU-1000: Structure and energetics', Journal of Physical Chemistry C, vol. 120, no. 30, pp. 16850-16862. https://doi.org/10.1021/acs.jpcc.6b05707
Lownsbury JM, Santos-López IA, Zhang W, Campbell CT, Yu HS, Liu WG et al. Calcium vapor adsorption on the metal-organic framework NU-1000: Structure and energetics. Journal of Physical Chemistry C. 2016 Aug 4;120(30):16850-16862. https://doi.org/10.1021/acs.jpcc.6b05707
Lownsbury, James M. ; Santos-López, Iván A. ; Zhang, Wei ; Campbell, Charles T. ; Yu, Haoyu S. ; Liu, Wei Guang ; Cramer, Christopher J. ; Truhlar, Donald G. ; Wang, Timothy ; Hupp, Joseph T ; Farha, Omar K. / Calcium vapor adsorption on the metal-organic framework NU-1000 : Structure and energetics. In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 30. pp. 16850-16862.
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